The direct synthesis of phenol from benzene in the gas phase was studied over hydroxyapatite catalysts. The reaction was carried out in a fixed-bed reactor at atmospheric pressure and reaction temperature of 450 degrees C in the presence of ammonia. A high selectivity (about 97%) of phenol formation at about 3.5% conversion of benzene was achieved over catalysts containing Ca and Cu ions in the cation part of hydroxyapatite. Besides phenol as the main reaction product. aniline is also formed. The reaction mechanism involves formation of N2O from NH3 in the first step of reaction. Benzene is oxidized by active oxygen species which are formed on the catalyst by decomposition of N2O.